Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

Tzu Hao Chiu; Jian Hong Liao; Franck Gam; Ying Yann Wu; Xiaoping Wang; Samia Kahlal; Jean Yves Saillard; C. W. Liu

doi:10.1021/jacs.2c03715

Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

Tzu Hao Chiu, Jian Hong Liao, Franck Gam, Ying Yann Wu, Xiaoping Wang, Samia Kahlal, Jean Yves Saillard, C. W. Liu

Single Crystal Diffraction

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Abstract

Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of the superatom core, but no accurate location of the hydride could be experimentally proved, so far. We report herein a hydride-doped eight-electron platinum/silver alloy nanocluster in which the position of four-coordinated hydride was determined by neutron diffraction for the first time. X-ray structures of [PtHAg₁₉(dtp/desp)₁₂] (dtp = S₂P(OⁿPr)₂, 1; dsep = Se₂P(OⁱPr)₂, 2) describe a central platinum hydride (PtH) unit encapsulated within a distorted Ag₁₂icosahedron, the resulting (PtH)@Ag₁₂core being stabilized by an outer sphere made up of 7 capping silver atoms and 12 dichalcogenolates. Solid-state structures of 1 and 2 differ somewhat in the spatial configuration of their outer spheres, resulting in overall different symmetries, C₁and C₃, respectively. Whereas the multi-NMR spectra of 2 in solution at 173 K reveal that the structure of C₃symmetry is the predominant one, ¹H and ¹⁹⁵Pt NMR spectra of 1 at the same temperature disclose the presence of isomers of both C₁and C₃symmetry. DFT calculations found both isomers to be very close in energy, supporting the fact that they co-exist in solution. They also show that the [PtH@Ag₁₂]⁵⁺kernel can be viewed as a closed-shell superatomic core, the μ₄-hydride electron contributing to its eight-electron count. On the other hand, the 1s(H) orbital contributes only moderately to the superatomic orbitals, being mainly involved in the building of a Pt-H bonding electron pair with the 5d_z²(Pt) orbital.

Original language	English
Pages (from-to)	10599-10607
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	144
Issue number	23
DOIs	https://doi.org/10.1021/jacs.2c03715
State	Published - Jun 15 2022

Funding

This work was supported by the Ministry of Science and Technology of Taiwan (MOST 109-2113-M-259-008), France-Taiwan ANR-MOST program (project Nanoalloys, ANR-18-CE09-0037-01), and the GENCI French National Computer Resource Center (A0030807367). Single-crystal neutron diffraction performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under contract no. DE-AC05-00OR22725 with UT-Battelle, LLC. We thank Academia Sinica High-Field NMR Center (HFNMRC) for technical support; HFNMRC is funded by Academia Sinica Core Facility and Innovative Instrument Project (AS-CFII-111-214).

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@article{b3192869653346818ef809521a8767c8,

title = "Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies",

abstract = "Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of the superatom core, but no accurate location of the hydride could be experimentally proved, so far. We report herein a hydride-doped eight-electron platinum/silver alloy nanocluster in which the position of four-coordinated hydride was determined by neutron diffraction for the first time. X-ray structures of [PtHAg19(dtp/desp)12] (dtp = S2P(OnPr)2, 1; dsep = Se2P(OiPr)2, 2) describe a central platinum hydride (PtH) unit encapsulated within a distorted Ag12icosahedron, the resulting (PtH)@Ag12core being stabilized by an outer sphere made up of 7 capping silver atoms and 12 dichalcogenolates. Solid-state structures of 1 and 2 differ somewhat in the spatial configuration of their outer spheres, resulting in overall different symmetries, C1and C3, respectively. Whereas the multi-NMR spectra of 2 in solution at 173 K reveal that the structure of C3symmetry is the predominant one, 1H and 195Pt NMR spectra of 1 at the same temperature disclose the presence of isomers of both C1and C3symmetry. DFT calculations found both isomers to be very close in energy, supporting the fact that they co-exist in solution. They also show that the [PtH@Ag12]5+kernel can be viewed as a closed-shell superatomic core, the μ4-hydride electron contributing to its eight-electron count. On the other hand, the 1s(H) orbital contributes only moderately to the superatomic orbitals, being mainly involved in the building of a Pt-H bonding electron pair with the 5dz2(Pt) orbital.",

author = "Chiu, {Tzu Hao} and Liao, {Jian Hong} and Franck Gam and Wu, {Ying Yann} and Xiaoping Wang and Samia Kahlal and Saillard, {Jean Yves} and Liu, {C. W.}",

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T2 - Structure, Bonding, and Multi-NMR Studies

AU - Chiu, Tzu Hao

AU - Liao, Jian Hong

AU - Gam, Franck

AU - Wu, Ying Yann

AU - Wang, Xiaoping

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Liu, C. W.

PY - 2022/6/15

Y1 - 2022/6/15

N2 - Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of the superatom core, but no accurate location of the hydride could be experimentally proved, so far. We report herein a hydride-doped eight-electron platinum/silver alloy nanocluster in which the position of four-coordinated hydride was determined by neutron diffraction for the first time. X-ray structures of [PtHAg19(dtp/desp)12] (dtp = S2P(OnPr)2, 1; dsep = Se2P(OiPr)2, 2) describe a central platinum hydride (PtH) unit encapsulated within a distorted Ag12icosahedron, the resulting (PtH)@Ag12core being stabilized by an outer sphere made up of 7 capping silver atoms and 12 dichalcogenolates. Solid-state structures of 1 and 2 differ somewhat in the spatial configuration of their outer spheres, resulting in overall different symmetries, C1and C3, respectively. Whereas the multi-NMR spectra of 2 in solution at 173 K reveal that the structure of C3symmetry is the predominant one, 1H and 195Pt NMR spectra of 1 at the same temperature disclose the presence of isomers of both C1and C3symmetry. DFT calculations found both isomers to be very close in energy, supporting the fact that they co-exist in solution. They also show that the [PtH@Ag12]5+kernel can be viewed as a closed-shell superatomic core, the μ4-hydride electron contributing to its eight-electron count. On the other hand, the 1s(H) orbital contributes only moderately to the superatomic orbitals, being mainly involved in the building of a Pt-H bonding electron pair with the 5dz2(Pt) orbital.

AB - Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of the superatom core, but no accurate location of the hydride could be experimentally proved, so far. We report herein a hydride-doped eight-electron platinum/silver alloy nanocluster in which the position of four-coordinated hydride was determined by neutron diffraction for the first time. X-ray structures of [PtHAg19(dtp/desp)12] (dtp = S2P(OnPr)2, 1; dsep = Se2P(OiPr)2, 2) describe a central platinum hydride (PtH) unit encapsulated within a distorted Ag12icosahedron, the resulting (PtH)@Ag12core being stabilized by an outer sphere made up of 7 capping silver atoms and 12 dichalcogenolates. Solid-state structures of 1 and 2 differ somewhat in the spatial configuration of their outer spheres, resulting in overall different symmetries, C1and C3, respectively. Whereas the multi-NMR spectra of 2 in solution at 173 K reveal that the structure of C3symmetry is the predominant one, 1H and 195Pt NMR spectra of 1 at the same temperature disclose the presence of isomers of both C1and C3symmetry. DFT calculations found both isomers to be very close in energy, supporting the fact that they co-exist in solution. They also show that the [PtH@Ag12]5+kernel can be viewed as a closed-shell superatomic core, the μ4-hydride electron contributing to its eight-electron count. On the other hand, the 1s(H) orbital contributes only moderately to the superatomic orbitals, being mainly involved in the building of a Pt-H bonding electron pair with the 5dz2(Pt) orbital.

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SN - 0002-7863

VL - 144

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EP - 10607

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

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